JPS63500185A - Manufacturing method, products and uses of high molecular weight polyimide - Google Patents
Manufacturing method, products and uses of high molecular weight polyimideInfo
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- JPS63500185A JPS63500185A JP61505868A JP50586886A JPS63500185A JP S63500185 A JPS63500185 A JP S63500185A JP 61505868 A JP61505868 A JP 61505868A JP 50586886 A JP50586886 A JP 50586886A JP S63500185 A JPS63500185 A JP S63500185A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 発明の名称 高分子量ポリイミドの製造方法、生成物及び用途［発明の背景コ １ 発明の技術分野 本発明はポリイミドの改良製造方法に関する。特に１本発明はジアンハイドライ ド及び相対的不反応性のジアミンから高分子量のポリイミドを製造することを可 能にするものである。[Detailed description of the invention] name of invention Production methods, products and uses of high molecular weight polyimides [Background of the invention] 1 Technical field of the invention The present invention relates to an improved method of manufacturing polyimide. In particular, one invention is dianhydride. It is possible to produce high molecular weight polyimides from diamines and relatively unreactive diamines. It is something that makes it possible.
２背景技術の説明 デュポン及びビロウは国際公開第Ｗ Ｏ８４−０２５２９号において太陽電池に カプセル化するに有用なポリイミド組成物被膜を開示している。その内容はここ に引用して挿入する。2. Explanation of background technology DuPont and Below have developed solar cells in International Publication No. W O84-02529. Polyimide composition coatings useful for encapsulation are disclosed. The contents are here Quote and insert.
上記デュポン及びビロウの特許出願のポリイミド被膜は次の反復単位を有するポ リイミド組成物から形成される。The polyimide coating of the DuPont and Billow patent application has the following repeating units: formed from a liimide composition.
■ であり、ｎは１〇−約２０００の考えられる値の範囲であり。■ and n ranges from 10 to about 2000 possible values.
好ましくは約１０−約１０００である。Preferably from about 10 to about 1000.
デュポン及びビロウの発明で最も好ましいポリイミドは。The most preferred polyimide according to DuPont and Billow's invention is:
上記式ＩＩのメタ アミノ フェニレン誘導体であり１次の反復構造単位を有し 。It is a meta-amino phenylene derivative of the above formula II and has a primary repeating structural unit. .
■ ■ 式中、ｎは上記の値である。■ ■ In the formula, n is the above value.
上記式Ｉのポリイミドは、実質的に等モル割合の２の単量体、２，２−ビス＝（ ３−又は４−アミノフェニル）へキサフルオロプロパン及び４．４−一へキサフ ルオロイソプロピリデン［ビス（フタリック アンハイドライド）〕との該単量 体に対する溶媒中での反応によって製造される。使用のために開示された溶媒は １例えば、ジメチルスルフオキシド。The polyimide of formula I above comprises substantially equimolar proportions of 2 monomers, 2,2-bis=( 3- or 4-aminophenyl) hexafluoropropane and 4.4-1-hexaf The monomer with fluoroisopropylidene [bis(phthalic anhydride)] It is produced by reaction in a solvent against the body. Solvents disclosed for use are 1 For example, dimethyl sulfoxide.
テトラヒドロフラン、Ｎ−メチルピロリジノン、Ｎ−メチルフォルムアミド、ジ メチルフォルムアミド及びＮ、Ｎ−ジメチルアセタミド及びその混合物を含む、 生成ポリアミド酸溶液はフィルムとして流し込し、該フィルムをイミド化し上記 Ｉのポリイミド構造にする。ポリアミド酸及びポリイミドの両者は少なくとも０ ．１９通常は０．３−０．５のインヘレント粘度を有することで特徴付けられる 。ポリイミドのインヘレント粘度は、冷製［９５％］硫酸又はメタンスルフォン 酸のような適当な溶媒の０．５％溶液として３０℃で測定する。Tetrahydrofuran, N-methylpyrrolidinone, N-methylformamide, di including methylformamide and N,N-dimethylacetamide and mixtures thereof; The resulting polyamic acid solution is poured as a film, and the film is imidized and the above-mentioned process is carried out. Make it a polyimide structure of I. Both polyamic acid and polyimide have at least 0 ．． 19 Usually characterized by having an inherent viscosity of 0.3-0.5 . The inherent viscosity of polyimide is determined by cold [95%] sulfuric acid or methanesulfone. Measured as a 0.5% solution in a suitable solvent such as an acid at 30°C.
被覆太陽電池の製造にあたって、上記式Ｖのポリアミド酸先駆体のテトラヒドロ フランのような溶媒の溶液、ポリアミド酸濃度的１０−約３０％、を太陽電池の 活性表面に適用するワニスとして用いている。In the production of coated solar cells, the polyamic acid precursor of formula V above is A solution of polyamic acid in a solvent such as furan, at a concentration of 10 to about 30%, is used in solar cells. It is used as a varnish applied to active surfaces.
太陽電池への、所望の場合プライマの上に、ポリアミド酸ワニスの適用後、溶媒 を実質的に蒸発させ、アミド酸重合体を約２５０℃に加熱してイミド化し式ＩＶ のポリイミド構造に変換する。１２０℃のような低い温度でも、イミド化を促進 するのに用いることができるが１反応速度は遅＜ ｔｉす、溶媒残留物の除去が 遅くなる。好ましいイミド化温度は約１６０−約２５０℃である。After application of polyamic acid varnish to the solar cell, if desired over the primer, solvent is substantially evaporated and the amic acid polymer is imidized by heating to about 250°C to form formula IV into a polyimide structure. Promotes imidization even at temperatures as low as 120℃ However, the reaction rate is slow and removal of solvent residues is difficult. Become slow. The preferred imidization temperature is about 160 to about 250°C.
デュポン及びビロウのポリイミドは、 （１）無色であり。DuPont and Billow's polyimides are (1) colorless;
（２）可視光の太陽照射に透明であり、 （３）相対的に跪くなく、（４）高度 の熱安定性を有し、（５）認識できる劣化がなく太陽照射を容易に透過し、（６ ）耐熱であり。(2) transparent to visible solar radiation, (3) relatively non-prone, and (4) high altitude. It has a thermal stability of (5), readily transmits solar radiation without appreciable degradation, and (6) ) It is heat resistant.
（７）紫外線にさらしたときほとんど劣化しないし。(7) It hardly deteriorates when exposed to ultraviolet light.
（８）電子及び低エネルギプロトン照射に対する保護に高度に有効である被覆を 提供する。(8) coatings that are highly effective in protecting against electron and low-energy proton radiation; provide.
然しながら、デュポン及びビロウの組成物は、得られる分子量がかなり低いため に、取扱い可能な、自由支持フィルムとして用いることができず、被膜の形態で 適用しなければならない、デュポン及びビロウの組成物は、所期の目的には満足 できるが、自由支持フィルム又は他の有用な形態で適用することができるポリイ ミド物質に対する需要は当該技術に存在する。However, the compositions of DuPont and Billows result in much lower molecular weights; However, it cannot be used as a handleable, free-supporting film, but in the form of a coating. The compositions of DuPont and Billows, which must be applied, are satisfactory for the intended purpose. polyimide, which can be applied in free-supporting films or other useful forms. A need exists in the art for mido materials.
［発明の概要］ 従って５本発明の目的は、ジアンハイドライド及び相対的不反応性のジアミンか ら形成される高分子量ポリイミド重合体を提供することにある。特に１本発明の 目的は、２．２−ビス（３−又は４−アミノフェニル）へキサフルオロプロパン ［以後「３−又は４−６Ｆ ジアミン」という］と４．４″−へキサフルオロイ ソプロピリデン［ビス−（フタリック アンハイドライド）コ［以後ｒ６ＦＤＡ Ｊという］とのポリ縮合による共重合によって形成されるポリイミドを提供する ものであり、該ポリイミドは先行技術の方法を用いて同一物質を共重合させて得 られるものより高い分子量に特徴を有するものである１本発明の他の目的は、３ −又は４−６Ｆ ジアミン及び６ＦＤＡがら得られる高分子全ポリイミドを製造 する方法に関する。[Summary of the invention] Therefore, it is an object of the present invention to combine dianhydrides and relatively unreactive diamines. An object of the present invention is to provide a high molecular weight polyimide polymer formed from the above. In particular, one invention The purpose is to obtain 2,2-bis(3- or 4-aminophenyl)hexafluoropropane. [hereinafter referred to as "3- or 4-6F diamine"] and 4.4''-hexafluoroyl Sopropylidene [bis-(phthalic anhydride) co] [hereinafter referred to as r6FDA A polyimide formed by copolymerization by polycondensation with and the polyimide is obtained by copolymerizing the same materials using prior art methods. 1. Another object of the present invention is that 3. -or Manufacture polymeric all-polyimide obtained from 4-6F diamine and 6FDA Regarding how to.
更に１本発明の目的は、３−又は４−６Ｆ ジアミン及び６ＦＤＡのポリイミド から形成され有用な形態に形成できる自由支持フィルムを提供することにある。A further object of the present invention is to prepare polyimides of 3- or 4-6F diamines and 6FDA. The object of the present invention is to provide a free-supporting film that can be formed from and formed into useful forms.
更に他の本発明の目的は、透明照射保護材料の薄いシートとして３−又は４−６ Ｆ ジアミン及び５ＦＤＡから形成されるポリイミドの自由支持フィルムを包含 する太陽電池を提供するものである。Yet another object of the invention is to provide 3- or 4-6 as a thin sheet of transparent radiation protection material. Contains a freely supported film of polyimide formed from F diamine and 5FDA The present invention provides a solar cell that can
本発明の他の目的は、明細書の記載から当業者には明らかであろう。Other objects of the invention will be apparent to those skilled in the art from the description.
本発明によれば１次の反復構造単位を包含するポリイミドは、溶媒中で２種の単 量体、３−又は４−６Ｆ ジアミン及び６ＦＤＡの実質的に等モル量を反応させ ることによって製造され１本改良は該溶媒としてクレゾールを用いることにある 。According to the present invention, a polyimide containing a first-order repeating structural unit is formed by two types of monomers in a solvent. 6FDA, 3- or 4-6F diamine, and substantially equimolar amounts of 6FDA are reacted. One improvement lies in the use of cresol as the solvent. .
■ 式中、Ｒは次のものである。■ In the formula, R is as follows.
本発明の好ましい態様においてはジアミンは３−６Ｆ ジアミンである。In a preferred embodiment of the invention, the diamine is a 3-6F diamine.
本発明の他の好ましい態様においては溶媒はメタ−クレゾールを包含する。In another preferred embodiment of the invention, the solvent includes meta-cresol.
更に１本発明の他の好ましい態様においては、クレゾール溶媒中で高分子量６ Ｆジアミン／６ＦＤＡ重合体を製造し。Furthermore, in another preferred embodiment of the present invention, high molecular weight 6 F diamine/6FDA polymer was produced.
次いで通常の溶媒溶液キャスチング法を用いて自由支持、非脆性、加工性フィル ムを形成することを包含する。このフィルムは太陽電池の活性表面への保護層と して用いることかできる。A free-supporting, non-brittle, processable film is then formed using a conventional solvent solution casting method. This includes forming a system. This film acts as a protective layer on the active surface of solar cells. It can be used as
［発明の詳細な説明］ 上述したように１次の構造を有するポリイミドは知られている。[Detailed description of the invention] As mentioned above, polyimides having a primary structure are known.
■ 式中、Ｒは次のものである。■ In the formula, R is as follows.
また、各単量体、２，２−ビス−（３−又は４−アミノフェニル）へキサフルオ ロプロパン及び４．４゛−へキサフルオロイソプロピリデン［ビス（フタリック アンハイドライド）］を上述の溶媒の存在下で、該反応体を室温で混合し。In addition, each monomer, 2,2-bis-(3- or 4-aminophenyl)hexafluoride lopropane and 4.4゛-hexafluoroisopropylidene [bis(phthalic) anhydride)] in the presence of the above-mentioned solvent, and the reactants are mixed at room temperature.
反応させることは知られている。実際、先行技術により生成する初期生成物はポ リイミドのポリアミド酸先駆体である。It is known to cause a reaction. In fact, the initial products produced by the prior art are It is a polyamic acid precursor of Riimide.
ポリアミド酸は溶媒蒸発後約２５０℃での加熱によってポリイミドに変換される 。Polyamic acid is converted to polyimide by heating at approximately 250°C after solvent evaporation. .
本発明のポリイミド製造方法の態様の実施にあたって、各単量体はこれまで溶媒 としてのクレゾールの置換で反応させ溶解を助けるため熱を用いてポリイミドを 形成させた。In carrying out embodiments of the polyimide production method of the present invention, each monomer has been Polyimide is reacted with cresol substitution using heat to aid in dissolution. formed.
十分には理解されていないが、クレゾールの使用はポリ縮合反応をデュポン及び ビロウの溶媒の使用で実際に到達する点以上に進行し、ポリイミド分子量を有用 な形態に製造できる自由支持フィルムを得ることができるレベルにまでもたらす 、さらにクレゾール溶媒の使用で溶液反応は先駆体ボリアクレゾールが６ＦＤＡ ／６Ｆジアミンポリイミド反応に作用する独特の効果を理解するために１次の因 子が関与していると考えられる。即ち、 （１）クレゾールは温和な酸性であり 、６Ｆジアミンの塩基性を薄める。 （２）クレゾールは高沸点を有し、先駆体 アミド酸から環状イミド構造の形成を容易にする。及び（３）クレゾールは反応 を完了させるに必要な上昇温度においてポリイミドと非反応性である。クレゾー ル溶媒においては、まずポリアミド酸が低温［はぼ周囲温度］で形成する。高温 度［２１０−２２０℃まで］に加熱すると。Although not well understood, the use of cresols has been shown to improve polycondensation reactions by DuPont and The use of billowy solvents actually progresses beyond the point reached and makes the polyimide molecular weight useful to a level where it is possible to obtain free-supporting films that can be manufactured into various forms. , furthermore, by using a cresol solvent, the solution reaction is possible when the precursor poly-cresol is 6FDA To understand the unique effects acting on the /6F diamine polyimide reaction, we It is thought that a child may be involved. That is, (1) Cresol is mildly acidic. , dilutes the basicity of 6F diamine. (2) Cresol has a high boiling point and is a precursor Facilitates the formation of cyclic imide structures from amic acids. and (3) cresol is a reaction is non-reactive with polyimide at the elevated temperatures required to complete the process. cresot In the solvent, the polyamic acid is first formed at low temperatures [nearly ambient temperature]. high temperature When heated to [210-220°C].
ポリアミド酸はポリイミドにシクロデヒドロ化する。ポリイミドはクレゾール溶 媒に完全に可溶である。Polyamic acid is cyclodehydrated to polyimide. Polyimide is dissolved in cresol. completely soluble in the medium.
本発明の６ Ｆ／６ Ｆ ＤＡポリイミドの特徴は１分子量が約１０．０００− １３０．０００．好ましくは約２５，０００−５０，０００ ［ｒｎｊは約１５ −２００．好ましくは約４０−８０］、及びインヘレント粘度が約０．１−０． ６゜好ましくは約０．４であることである。インヘレント粘度は。The 6F/6F DA polyimide of the present invention is characterized by a molecular weight of approximately 10.000- 130.000. Preferably about 25,000-50,000 [rnj is about 15 -200. 40-80] and an inherent viscosity of about 0.1-0. 6°, preferably about 0.4. What is the inherent viscosity?
Ｎ、Ｎ−ジメチル アセトアミド、又はテトラヒド口フランのような適当な溶媒 の０．５％溶液として３０℃で測定する。A suitable solvent such as N,N-dimethyl acetamide or tetrahydrofuran Measured as a 0.5% solution at 30°C.
ここで用いる「クレゾール」の語は、オルト−クレゾール。The term "cresol" as used herein refers to ortho-cresol.
メタ−クレゾール、パラ−クレゾール、又はその混合物を含むものである１本発 明の実施において、メタ−クレゾールが好ましい、クレゾール異性体のうちで最 も除き易いし有害となる得る残留物を残さないからである９例えば、バラ−クレ ゾールを酸化すると着色物質が生じ、これは所望のポリイミながら、不純物を含 んでいる市販グレードの物質は本発明の実施に用いることができる。市販グレー ドの「クレゾール」はしばしば３異性体プラス不純物の混合物である。市販グレ ードのクレゾールを乾燥し真空蒸溜して水及び着色不純物を除くことは好ましい 。One bottle containing meta-cresol, para-cresol, or a mixture thereof In the present practice, meta-cresol is the most preferred of the cresol isomers. This is because it is easy to remove and does not leave any harmful residue9. Oxidation of the sol produces a colored material, which is the desired polyimide but contains impurities. Commercially available materials containing materials can be used in the practice of this invention. commercially available gray "Cresol" is often a mixture of three isomers plus impurities. Commercial gray It is preferable to dry the cresol and vacuum distill it to remove water and colored impurities. .
更に１本発明の実施に用いるクレゾール溶媒は、高分子量ポリイミドの製造に悪 影響を与えず、かつポリイミド生成物を形成する反応を生じるのに必要な温度と 適合できる沸点を有する共溶媒と混合することができる。典型的な共溶媒にはベ ンゼン、トルエン、及びキシレンがある。更に、後者の共溶媒は、共沸蒸溜によ って反応から水を除去させて水による重合体の分解を妨げることによって重合体 生成物の生成を容易にすることができる。共溶媒は、触媒作用によって本発明に よる所望の結果を達成するクレゾール成分と共に反応溶媒の９５容量％まで存在 することができる。Furthermore, the cresol solvent used in the practice of the present invention is harmful to the production of high molecular weight polyimide. temperature and temperature necessary to cause the reaction to form the polyimide product without It can be mixed with co-solvents with compatible boiling points. Typical co-solvents include toluene, and xylene. Furthermore, the latter co-solvent can be removed by azeotropic distillation. polymer by removing water from the reaction and preventing water from decomposing the polymer. Product production can be facilitated. Co-solvents contribute to the invention through catalytic action. up to 95% by volume of the reaction solvent with the cresol component to achieve the desired result. can do.
ポリイミドは、そのクレゾール溶液を絶対メタノール又はエタノールのような十 分の非溶媒と混合するか、又は真空蒸溜によってクレゾール溶媒を追出すことに よって単離することができる。その後所望ならば更に精製し、フィルムを標準溶 媒フィルムキャスティング法で形成することができる１例えば２重合体をジメチ ルアセトアミド又はジメチルアセトアミドとアセトンの混合物に溶解した後、静 止又は移動混晶体上にキャスティングし加熱して残留溶媒を除くのである。再生 可能な透明フィルムが得られ１個別太陽電池の水晶又はガラスカバーの代わりに 用いることができる。テトラヒドロフラン、アセトン、ジメチルアセトアミドの ような溶媒、同様な溶媒又は混合物と共にラッカーの形態でポリイミドを用いて 太陽電池に該フィルムを接着することができる。For polyimide, its cresol solution must be completely diluted with methanol or ethanol. The cresol solvent can be driven off by mixing with a minute non-solvent or by vacuum distillation. Therefore, it can be isolated. Thereafter, if desired, further purification is performed to convert the film into a standard solution. For example, a dimethyl dipolymer can be formed by a medium film casting method. After dissolving in acetamide or a mixture of dimethylacetamide and acetone, The residual solvent is removed by casting on a stationary or moving mixed crystal and heating. reproduction A possible transparent film can be obtained in place of the crystal or glass cover of one individual solar cell. Can be used. of tetrahydrofuran, acetone, dimethylacetamide using polyimide in the form of a lacquer with similar solvents or mixtures such as The film can be adhered to a solar cell.
次に限定的ではない例をあげて本発明の製造方法を説明する。Next, the manufacturing method of the present invention will be explained by giving a non-limiting example.
例１ １００ｍ、丸底３つ首フラスコに、油浴、磁気撹拌機。Example 1 100 m, round bottom three neck flask, oil bath, magnetic stirrer.
還流コンデンサ、窒素気体入口、水銀バブラへの窒素気体出口を取付けた６ こ のフラスコに６ＦＤＡ Ｃ４，４４ｇ。This 6-piece is equipped with a reflux condenser, nitrogen gas inlet, and nitrogen gas outlet to the mercury bubbler. 6FDA C4, 44g in a flask.
０．０１０モルコ及び新たに蒸溜し乾燥したメタ−クレゾール［３５１ｊＪ！］ を入れた。６ＦＤＡは明黄色溶液を形成し、溶液とするにはメタ−クレゾールを 温めることが必要であった。0.010 molco and freshly distilled and dried meta-cresol [351jJ! ] I put it in. 6FDA forms a bright yellow solution, which requires meta-cresol to form a solution. It was necessary to warm it up.
溶液は室温に冷却し、３−６Ｆジアミン［３，３４ｇ。The solution was cooled to room temperature and the 3-6F diamine [3.34 g.
０．０１０モル］を少しずつ加えた。溶液は周囲温度で３０分間撹拌し、油浴を フラスコの下においた１反応混合物は窒素下で２１０−２２０℃の油浴温度で加 熱した。加熱の初期には泡立ちがあった。おそらくはイミド化工程からの水の放 出によるものである３反応混合物は１時間加熱し２周囲温度に冷却し、絶対メタ ノール中に注いで重合体を単離した１重合体は漏逸し、新鮮なメタノールで洗浄 し、９０℃で真空乾燥した８重合体は次いで２００＋ｕ！のテトラヒドロフラン に溶解し、数ｇの活性炭で処理し、漏逸し、容量を７５ｍに減少した１次いで２ ００ｄの絶対メタノールを加え沈澱重合体を漏逸した９重合体をメタノールで洗 浄し１００℃で乾燥して４．１ｇを得た９分子ｆｆｉ ［Ｍｗ］は３４，４００ であった。0.010 mol] was added little by little. The solution was stirred for 30 minutes at ambient temperature and removed from the oil bath. 1 The reaction mixture placed at the bottom of the flask was heated under nitrogen at an oil bath temperature of 210-220°C. It was hot. There was bubbling at the beginning of heating. Probably due to water release from the imidization process. The reaction mixture was heated for 1 hour, cooled to ambient temperature, and the absolute methane The polymer was isolated by pouring it into alcohol. The polymer leaked out and was washed with fresh methanol. Then, the octapolymer dried in vacuum at 90°C was 200+u! of tetrahydrofuran 1 and then 2 which were dissolved in water and treated with several grams of activated carbon, which leaked and reduced the capacity to 75 m. 00d of absolute methanol was added and the precipitated polymer was washed with methanol to remove the leaked 9 polymer. 9 molecules ffi [Mw] obtained by cleaning and drying at 100°C to obtain 4.1 g is 34,400 Met.
放置後、追加の重合体が溶液から生じた３分子量は１３．８００．良質の無色自 由支持フィルムが３４，４００Ｍｗ重合体からジメチルアセタミドに溶解し強制 空気炉で１００℃次いで窒素下で３００℃まで加熱して得られた。フィルムは、 空気中３００℃に加熱すると、はとんど色変化を示さなかった。これは３００℃ 熱処理後ジメチルアセタミド及びアセトンに可溶であり、この物質をポリイミド の中でも特異なものとした。約０．１−２．０ミル［２，５４ｘ１０４乃至５． ０８ｘ １０’ ｃｍ］の厚さのフィルムを太陽電池の活性表面を保護するの に用いることができた。After standing, the additional polymer produced from the solution has a molecular weight of 13.800. good quality colorless A support film of 34,400 Mw was dissolved in dimethyl acetamide and forced. It was obtained by heating in an air oven to 100°C and then to 300°C under nitrogen. The film is When heated to 300° C. in air, it showed almost no color change. This is 300℃ After heat treatment, it is soluble in dimethylacetamide and acetone, and this substance can be converted into polyimide. It was made unique among all. Approximately 0.1-2.0 mil [2.54 x 104 to 5. 08 x 10’ cm] thick film to protect the active surface of the solar cell. It could be used for.
本発明の変形は当業者に明らかであろう１例えば１本発明の高分子量ポリイミド はその溶液からまず自由支持性フィルムを形成することなく直接太陽電池のよう な基体上にキャスティングすることができる１本発明のポリイミドフィルムは。Variations of the invention will be apparent to those skilled in the art, for example one of the high molecular weight polyimides of the invention. directly from its solution without first forming a freely supporting film, such as a solar cell. One polyimide film of the present invention that can be cast onto a substrate is:
半導体部品製造のアルファ粒子バリヤーとしての用途を含み。Including use as an alpha particle barrier in semiconductor component manufacturing.
印刷回路工業のような他の用途に用いることができる。これらの用途では、ある 場合には自由支持フィルムが用いられ。It can be used in other applications such as the printed circuit industry. In these applications, there are In some cases, free supporting films are used.
他の場合には重合体溶液が浸漬、電子被覆、噴霧、静電噴霧等によって適用され る。このポリイミドは種種な製造技術に役立つ、また、ポリイミドの特異な溶解 特性は、汚染ガラス窓のような保存技術物品のような他の用途を示唆する。In other cases, polymer solutions are applied by dipping, electrocoating, spraying, electrostatic spraying, etc. Ru. This polyimide is useful in a variety of manufacturing techniques, and its unique solubility The properties suggest other uses such as conservation technology articles such as contaminated glass windows.
国際調査報告 ＡＮＮ″−Ｘ Ｔｏ ｉ：：Ｅ Ｉ！ＪＴＥ：４３：ＡＴＩＯＮＡＬ ５ＥＡＲ ＣＨＲＥ？ＯＲＴ ＯＮinternational search report ANN''-X Toi::E I!JTE:43:ATIONAL 5EAR CHRE? ORT ON
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US801433 | 1985-11-25 | ||
| US06/801,433 US4645824A (en) | 1985-11-25 | 1985-11-25 | Method of preparing high molecular weight polyimide, product and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63500185A true JPS63500185A (en) | 1988-01-21 |
Family
ID=25181080
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61505868A Pending JPS63500185A (en) | 1985-11-25 | 1986-09-15 | Manufacturing method, products and uses of high molecular weight polyimide |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4645824A (en) |
| EP (1) | EP0247084A1 (en) |
| JP (1) | JPS63500185A (en) |
| CA (1) | CA1262993A (en) |
| WO (1) | WO1987003289A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02208324A (en) * | 1989-02-08 | 1990-08-17 | Nitto Denko Corp | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
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|---|---|---|---|---|
| US5428102A (en) * | 1987-07-15 | 1995-06-27 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Low dielectric polyimides |
| US5338826A (en) * | 1987-07-15 | 1994-08-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administation | Structures from low dielectric polyimides |
| US4996278A (en) * | 1988-02-09 | 1991-02-26 | Occidental Chemical Corporation | Novel polyimidesiloxanes and methods for their preparation and use based on diamines with pendant fluorine groups |
| US4978738A (en) * | 1988-07-12 | 1990-12-18 | Hoechst Celanese Corp. | High molecular weight, thermally soluble polyimides |
| US5049649A (en) * | 1988-07-12 | 1991-09-17 | Hoechst Celanese Corp. | Colorless films formed from fluorinated polyimides |
| JPH0286624A (en) * | 1988-07-12 | 1990-03-27 | Hoechst Celanese Corp | High-molecular weight polyimide, its preparation, and molded article thereof |
| US5026822A (en) * | 1988-07-12 | 1991-06-25 | Hoechst Celanese Corp. | High molecular weight polyimide, method of making same and articles formed therefrom |
| DE3833338A1 (en) * | 1988-09-30 | 1990-05-31 | Hoechst Ag | FLUORINE MONOMERS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US5077370A (en) * | 1988-11-14 | 1991-12-31 | Occidental Chemical Corporation | Novel polyimidesiloxanes and methods for their preparation and use |
| USRE33797E (en) * | 1988-11-14 | 1992-01-14 | Occidental Chemical Corporation | Novel polyimidesiloxanes and methods for their preparation and use |
| CA2009085A1 (en) * | 1989-02-27 | 1990-08-27 | Rohitkumar H. Vora | Coatings of intermediate molecular weight polyimides |
| US4933132A (en) * | 1989-02-28 | 1990-06-12 | Hoechst Celanese Corp. | Process of making a shaped article from intermediate molecular weight polyimides |
| US4954609A (en) * | 1989-02-28 | 1990-09-04 | Hoechst Celanese Corp. | Intermediate molecular weight fluorine containing polymide and method for preparation |
| US5055116A (en) * | 1989-05-22 | 1991-10-08 | Hoechst Celanese Corp. | Gas separation membranes comprising miscible blends of polyimide polymers |
| JP3361755B2 (en) | 1998-08-17 | 2003-01-07 | 財団法人石油産業活性化センター | Method for selective separation of hydrocarbons |
| EP2433978B1 (en) * | 2007-09-07 | 2016-07-27 | NeXolve Corporation | Polyimide polymer with oligomeric silsesquioxane |
| US8309627B2 (en) | 2007-09-07 | 2012-11-13 | Nexolve Corporation | Polymeric coating for the protection of objects |
| KR101543478B1 (en) | 2010-12-31 | 2015-08-10 | 코오롱인더스트리 주식회사 | Transparent Polyimide film and Method for Preparing the Same |
| KR101509831B1 (en) | 2010-12-31 | 2015-04-08 | 코오롱인더스트리 주식회사 | Method for Preparing Polyimide Film |
| CN105190412B (en) | 2013-05-08 | 2018-10-16 | 英派尔科技开发有限公司 | Polarizing liquid crystal both alignment layers and display |
| WO2015099478A1 (en) | 2013-12-26 | 2015-07-02 | 코오롱인더스트리 주식회사 | Transparent polyamide-imide resin and film using same |
| KR102227672B1 (en) | 2014-12-31 | 2021-03-16 | 코오롱인더스트리 주식회사 | Polyamide-imide precursor composition, polyamide-imide film and display device |
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- 1985-11-25 US US06/801,433 patent/US4645824A/en not_active Expired - Fee Related
-
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- 1986-09-15 JP JP61505868A patent/JPS63500185A/en active Pending
- 1986-09-15 EP EP86906518A patent/EP0247084A1/en not_active Withdrawn
- 1986-09-15 WO PCT/US1986/001901 patent/WO1987003289A1/en not_active Application Discontinuation
- 1986-11-24 CA CA000523657A patent/CA1262993A/en not_active Expired
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| JPS5120080A (en) * | 1974-08-12 | 1976-02-17 | Suzumo Kikai Kogyo Kk | MIZUBUNKAISOCHINIOKERU HOANSOCHI |
| JPS5230319A (en) * | 1975-09-04 | 1977-03-08 | Nippon Hoso Kyokai <Nhk> | Compensation circuit of digital type gamma |
| JPS5953286A (en) * | 1982-09-20 | 1984-03-27 | ヤマハ発動機株式会社 | Front suspension system for motorcycle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH02208324A (en) * | 1989-02-08 | 1990-08-17 | Nitto Denko Corp | Low-permittivity sheet, and laminate and multilayer circuit board prepared by using same sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987003289A1 (en) | 1987-06-04 |
| EP0247084A1 (en) | 1987-12-02 |
| CA1262993A (en) | 1989-11-14 |
| US4645824A (en) | 1987-02-24 |
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